JP3002515B2 - Novel alkyl carbamate, method for producing the same, aqueous wax microdispersion and cosmetic composition - Google Patents

Abstract

Compounds of formula R-NHCOOCH(CH2OCH2CHOHCH2OH)2 (I> in which R is an optionally unsaturated C10-20alkyl; their preparation and their application as surfactants or emulsifiers, in particular in the preparation of wax microdispersions which are especially usable as cosmetic compositions for the hair.

Description

The present invention relates to novel esters of polyols, their preparation and, in particular, their use as surfactants.

French Patent 2,549,286 (84.11687) describes monoethers of fatty alcohols and triglycerol, which are mainly useful as surfactants in cosmetic compositions, and bis (isopropylidene) derivatives of linear triglycerol, The preparation of the above monoethers in a well-defined form is described.

It has now been found that certain triglycerol alkyl carbamates exhibit interesting surfactant properties which allow the compounds to be used primarily for the preparation of cosmetic compositions.

On the other hand, the use of certain waxes enables stable and infinitely dilutable microdispersions with water without agglomeration or settling of the particles in suspension.
It is known that n) can be obtained. A microdispersion of wax is obtained by melting the wax in the presence of a surfactant and optionally a portion of water and then continuously adding hot water with stirring. Intermediately, a water-in-oil emulsion is formed, followed by a phase change, which ultimately results in an oil-in-water emulsion. Upon cooling, a stable microdispersion of solid colloidal wax is obtained (LMPrince bias, “Microemulsions Theory and Pr.
actice ", Academic Press (1977), pp. 21-32.)

From the research results of the present inventor, it was recognized that a wax microdispersion could not be obtained when the monoether of triglycerol disclosed in the above-mentioned French patent specification was used.

In contrast, it has been found that a wax microdispersion can be produced by using the triglycerol alkyl carbamate of the present invention.

Such wax microdispersions are primarily useful as supports for hair cosmetic compositions. This use was filed on February 24, 1989, and was filed as “Use as cosmeti
c composition for the hair, a wax microdispersion, a
nd process for the treatment of hair with such ac
Luxembourg Patent Application No. 87,457 entitled "omposition"
Form the gist of the issue.

Further, triglycerol alkyl carbamates
It has also been found to show improved skin resistance as compared to the ethers disclosed in said French patent specification.

Accordingly, the present invention provides a compound of the formula (I): R-NHCOOCH (CH ₂ OCH ₂ CHOHCH ₂ OH) ₂ (I) wherein R is a saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms. Which represents an alkyl carbamate.

In the formula (I), the R groups are, in particular, n-decyl, n-
Dodecyl, n-tetradecyl, n-hexadecyl, n-
Octadecyl, n-octadecenyl (oleyl), 2-
It may represent a hexyldecyl, 2-octyldodecyl or 2-heptylundecyl group.

The invention further relates to a process for preparing the compound of formula (I).

"This method has the formula _{(II A): R 1 CH} 2 CH (R 2) CH 2 OCH 2 CH (OR 6) CH 2 OCH 2 CH (R 2) CH 2 R
₁ (II A) wherein R ₁ and R ₂ are taken together with the formula: —O—CR ₃ (R ₄ ) —O— (wherein R ₃ and R ₄ are each a lower alkyl group Represent)
Wherein R ₆ has the formula: And the amine RNH ₂ (R
Has the meaning according to claim 1) to obtain a compound of formula (III): R ₁ CH ₂ CH (R ₂ ) CH ₂ OCH ₂ CH (OR ₅ ) CH ₂ OCH ₂ CH (R ₂ ) CH ₂ R
₁ (III) wherein R ₅ represents -CONHR, and then the compound of formula (III) is hydrolyzed,
To obtain the corresponding compound of formula (I).

R ₆ has the formula: The imidazolide of formula (II A), which is a group of formula (II A), is represented by formula (II): R ₁ CH ₂ CH (R ₂ ) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (R ₂ ) CH ₂ R ₁
It can be prepared by reacting the compound of (II) with carbonyldiimidazole. The reaction of carbonyldiimidazole with the compound of formula (II) is carried out by dissolving these reactants in a solvent such as tetrahydrofuran or dichloromethane. The resulting solution is stirred for several hours at a temperature between 20 ° C. and the boiling point of the solvent. The resulting imidazolide of formula (III) can be used directly for the next reaction.

Starting from compound (II), according to known methods, R ₆
The corresponding chloroformate of formula (IIA) can be prepared where is -COCl.

For reaction with an amine, the compound of formula (IIA) is dissolved in a solvent such as dichloromethane. Then amine RN
Adding of H ₂ for example in the form of a solution in dichloromethane. When compound (IIA) is a chloroformate, the reaction is performed in the presence of an HCl receptor, such as pyridine or triethylamine. The reaction medium is stirred for several hours at a temperature between, for example, 20 ° C. and the boiling point of the solvent. The organic phase is then washed several times with water and dried, for example, over sodium sulfate. The solution is then removed by evaporation under reduced pressure. The resulting formula (II
The compounds of I) can be directly subjected to hydrolysis.

The hydrolysis is carried out, for example, with a small amount of water and a protonated acid (prot acid).
The reaction is carried out in a solvent such as methanol, ethanol or tetrahydrofuran in the presence of an onated acid).

Inorganic acids such as sulfuric acid, phosphoric acid or hydrochloric acid or organic acids such as p-toluenesulfonic acid may be used. Preferably, hydrochloric acid is used.

The amount of acid may vary, for example, in the range from 0.05 to 0.2 mol, preferably from 0.05 to 0.1 mol, based on the number of moles of the compound of the formula (III).

The starting materials used in the process according to the invention are known compounds or can be prepared in a known manner. Diisopropylidene triglycerol (Formula II, R ₃ = R ₄ = methyl) is a commercial product from Solvay.

The invention further relates to the use of the compounds of the formula (I) as surfactants, in particular as emulsifiers in cosmetic compositions or in the support of cosmetic compositions. A particularly interesting application of the compounds of formula (I) is as a dispersant in aqueous wax microdispersions.

A process for preparing a wax microdispersion from a compound of formula (I) comprises the step of heating the wax and at least one compound of formula (I), optionally in the presence of a portion of water, at a temperature above the melting temperature of the wax. However, heating is performed at a temperature not higher than 100 ° C. until the wax is completely melted. Water or the rest of the water is added continuously; the temperature of the water is at least equal to the temperature at which the wax is heated. The mixture is then agitated until a wax microdispersion in the continuous aqueous phase is formed. The resulting wax microdispersion is then cooled to ambient temperature.

The invention further relates to a wax microdispersion obtainable by the above method.

Waxes that can be used are higher than
Waxes or wax mixtures having a final melting point below 100C.

The emulsifier consists of at least one compound of the formula (I) and optionally other nonionic or anionic emulsifiers mixed therewith.

The microdispersion is, for example, 0.1 to 40% by weight of wax and
0.01 to 25% by weight of an emulsifier.

Preferably, the weight ratio of wax / emulsifier is varied between 1 and 30.

Typically, the wax microdispersion contains at least 35% water.

In the obtained wax microdispersion, the particle size of the wax particles is 500 nm or less.

Waxes which can be used include, for example, carnauba wax, candelilla wax, alfa wax (Alfawax) and mixtures thereof.

The above waxes or mixtures thereof may be used in combination with other waxes or mixtures of other waxes, for example paraffin wax; the amount of carnauba wax and / or candelilla wax in such a mixture is preferably greater than or equal to 50% by weight .

Surfactants which can be used in admixture with the compounds of the formula (I) are, for example, 10-40 hydrophilic-lipophilic balances (HLB)
Is an anionic surfactant having the following formula: These surfactants are, in particular, organic salts such as salts of fatty acids, for example alkali salts or amines, which have, for example, from 12 to 18 carbon atoms and a double bond, as in oleic acid. Or a salt of an alkylsulfuric acid or alkylsulfonic acid having 12 to 18 carbon atoms or an alkylarylsulfonic acid having an alkyl chain having 6 to 16 carbon atoms or a salt of an organic base (the aryl moiety described above). Is, for example, a phenyl group). Surfactants may also be ether sulfates, especially those whose aliphatic chains have from 6 to 20 carbon atoms and whose polyalkosylated chains have from 1 to 30 oxyalkylene units, especially oxyethylene, oxypropylene or oxybutylene units. Is the product of the sulfation of fatty alcohols and polyalkoxylated alkylphenols.

Nonionic surfactants which can be used in admixture with the compounds of the formula (I) are, in particular, polyalkoxylated and / or polyglycerolated fatty acids or fatty acid amides; polyalkoxylated and / or polyglycerolized, Esters of fatty acids and polyols; polyalkoxylated and / or polyglycerolated fatty alcohols or alkylphenols; polyalkoxylated and / or polyglycerolated alkanediols or 1,2- or 1,3-
Alkenediol: polyalkoxylated and / or polyglycerolized alkanediol or 1,2
Or an alkyl ether of a 1,3-alkenediol. An optionally unsaturated fatty acid or fatty alcohol has, for example, 12 to 24 carbon atoms, the alkyl chain of the alkylphenol has, for example, 6 to 16 carbon atoms, and an alkanediol or alkenediol. has a 9 to 24 carbon atoms, although the number of the alkyl chain has 4 to 20 carbon atoms and oxyalkylene units or (-CH ₂ CHOH-CH ₂ O units of alkyl ether It can be 2 to 40.

Polyalkoxylated nonionic derivatives are, in particular,
A polyoxyethylenated derivative, optionally polyoxypropylene.

Polyalkoxylated fatty acids are commercially available products, especially sold under the trade name "Myrj" by ICIAMERICAS.

Polyoxyethylenated fatty alcohols are commercially available products, especially sold by ICIAMERICAS under the trade name "Briz".

Esters of polyols with polyoxyethylenated fatty acids, wherein the polyol is sorbitol, are in particular I.
This product is sold by CI AMERICAS under the trade name "Tween".

Polyglycerolated fatty alcohols, polyglycerolated alkane diols or alkene diols, or polyglycerolized alkane diols or alkyl ethers of alkene diols are, for example, French Patents 1,477,048, 2,025,681 and 2,465,780.
It can be prepared according to the methods described in this specification or methods analogous thereto.

Polyglycerolized fatty acids or fatty acid amides are described in particular in French Patent 1,484,723 or under the trade name "Plurol" from the company Gattefosse and under the trade name "Drewpol" from the company Stefan. It is a commercial product as sold.

The invention also relates to a cosmetic composition, in particular a hair cosmetic composition, characterized in that it contains at least one compound of the formula (I) as surfactant or emulsifier.

However, the cosmetic compositions of the present invention may contain conventional active ingredients, vehicles and second components which it is desirable to include in the composition.

The cosmetic composition of the present invention can be provided in particular in the form of a stable wax microdispersion as described above. These compositions in the form of wax microdispersions are particularly useful as styling lotions and lotions for improving the appearance of human hair with oily hair, as described in the aforementioned Luxembourg patent application.

These compositions in the form of a microdispersion may contain one or more of the conventional second components such as thickeners, stabilizers, fragrances and preservatives.

These second components may be added to the raw material components (prior to preparing the microdispersion) or may be added to the final composition, as the case may be.

Optionally, non-volatile, water-soluble components can be added to the water used to prepare the microdispersion.

The liposoluble component is usually added to the wax before preparing the microdispersion.

These compositions may be applied to dry or wet hair, for example, before or after shampooing. These compositions may be rinsed or non-rinsed and may be applied daily.

When these compositions are applied before or after shampooing and are rinsed with water or not soaked, they provide good descipline and styling hold and volume. Is given. Furthermore, these cosmetic compositions delay the phenomenon of hair becoming oily again, which is observed in people with oily hair.

The cosmetic composition of the present invention has a pH of 3-10. This pH
May optionally be adjusted using conventional pH adjusters.

 Hereinafter, examples of the present invention will be described.

Example 1 Preparation of a compound of formula (I) wherein R = hexadecyl group (a) Preparation of imidazolide 102 g (0.63 mol) of carbonyldiimidazole was charged to 500 c
Dissolved in m ³ dichloromethane. 200 g (0.
62 mol) of diisopropylidene triglycerol (Solv
500 cm ³ of dichloromethane (commercially available from ay) was added. The reaction medium is stirred for 5 hours at ambient temperature and then
Washed 4 times with m ³ water. The reaction medium was then dried over sodium sulfate and the solvent was evaporated under reduced pressure. 241 g of an oily compound were obtained; the purity of this compound was sufficient for use in the next reaction.

(B) Reaction with hexadecylamine 14.1 g (0.034 mol) of the imidazolide prepared above was added to 50
Dissolved in cm ³ of dichloromethane. This solution was dissolved in 25 cm ³ of dichloromethane. 7.2 g (0.03 mol) of hexadecylamine were added. The reaction medium was then stirred at ambient temperature overnight. The reaction medium was then washed several times with water. The organic phase was dried over sodium sulfate and the solvent was evaporated under reduced pressure to recover 20 g of a waxy compound.

(C) Hydrolysis 20 g of the waxy compound obtained in the above step was added to 2 cm ³
Was dissolved in 100 cm ³ of methanol to which 5N HCl was added. The reaction mixture was stirred overnight. After filtering out a small amount of insoluble matter,
The solvent was removed under reduced pressure. 17 g of a waxy product were obtained, which was recrystallized in a 200: 30 mixture of heptane and ethyl acetate.

At 0.5%, 13 g of a white wax having a Kraft point of 21-24 ° C and a cloud point above 100 ° C was obtained. This product corresponds to the compound of formula (I) where R is a hexadecyl group. ¹ H and ¹³ C NMR spectra were consistent with the assigned structure. Elemental analysis Theoretical value Found C% 61.51 61.2 H% 10.52 10.23 N% 2.76 2.63 Example 2 R is the formula compound example 1 diisopropylidene triglycerol prepared in (a) of (I) dodecyl To a 100 cm ³ solution of dichloromethane containing 54 g (0.13 mol) of imidazolide, 19.65 g (0.106 mol) of dodecylamine dissolved in 150 cm ³ of dichloromethane was added. The reaction medium was stirred overnight at ambient temperature and the reaction medium was washed three times with 100 cm ³ of water. The reaction medium was dried over sodium sulfate and the solvent was evaporated under reduced pressure.
62 g of a very slightly colored viscous oil were recovered.

60 g of this oily product was dissolved in 300 cm ³ of methanol and 5 cm ³ of 5N HCl was added. The reaction mixture was then stirred overnight at ambient temperature, and the solvent was evaporated under reduced pressure to give 49.2 g of a viscous oil. 30 g of this oil were purified on a silica column (Kieselgel 60, Merck) using a 90:10 mixture of dichloromethane: methanol as eluent.

12 g of the compound of formula (I) in which R is a dodecyl group were obtained in the form of a white wax.

^{The 13} C NMR spectrum was consistent with the assigned structure.

EXAMPLE 3 R is a diisopropylidene triglycerol prepared in Preparation Example 1 (a) but compounds of formula (I) is an oleyl group imidazolide in dichloromethane solution 100 cm ³ containing 5 g (0.12 mol), 100 cm ³ 26.75 g (0.1 mol) of oleylamine dissolved in dichloromethane. The reaction mixture was stirred for 5 hours and the solvent was removed under reduced pressure. 76 g of oil was recovered, which was
Purified by passing through a fritted glass filter packed with 60H silica (Merck) and eluting with a 9: 1 mixture of dichloromethane and methanol.

The solvent was removed under reduced pressure to recover 66 g of an oily compound. 60 g of this oil is taken up in 250 cm in the presence of 30 cm ³ of 1N HCl
Dissolved in ethanol of ³ and hydrolyzed by heating the reaction medium at 60 ° C. for 4 hours.

The solvent was removed under reduced pressure and the resulting waxy material was
Purified by passing through a fritted glass filter packed with eselgel 60H silica and eluting with a 95: 5 mixture of dichloromethane and methanol.

40 g of the compound of the formula (I) in which R is an oleyl group are obtained in the form of a translucent wax.

^{The 13} C NMR spectrum was consistent with the assigned structure.

Examples AD Preparation of Wax Microdispersion A wax microdispersion was prepared according to the method described above. Candelilla wax was used as the wax. The compound of formula (I) was used as emulsifier. Constituents of dispersion, amount thereof and physics of obtained wax microdispersion
The chemical properties (appearance, average particle size of wax particles, polydispersity) are shown in the table below.

For comparison, under the same conditions using a compound of the formula: C ₁₆ H ₃₃ OCH (CH ₂ OCH ₂ CHOHCH ₂ OH) ₂ as emulsifier (emulsifier: 1.93%;
KOH: 0.03%, wax: 10%) and a wax microdispersion were prepared. No microdispersion was obtained.

Examples CC1 to CC5 Preparation of Cosmetic Composition Example CC1 A hair care cosmetic composition was prepared by blending the following ingredients with the wax microdispersion: 98 g of the wax microdispersion prepared in Example A. Hydroxypropyl methylcellulose (Dow Chemical, “METHOCEL F4M”) 1.5 g Methyl p-hydroxybenzoate 0.2 g Imidazolidinyl urea derivative (Sutton Labs, “GER
MALL 115 ") 0.3 g The composition was applied to clean, dry hair, taking care to spread it over the length of the hair. 2 per head
55 g of the composition was used. The hair had swelling and the hair was well-shaped.

Example CC2 A composition for hair wash pretreatment in the form of a fluid gel was prepared by blending the following components with the wax microdispersion.

Wax microdispersion prepared in Example B 20 g Crosslinked polyacrylic acid (molecular weight 1,250,000) (Goodrich, "CARBOPOL 941") 1 g Imidazolinyl urea derivative (Sutton Labs, "GER"
MALL 115 ") 0.3 g Amount to make sodium hydroxide pH = 7 Water Amount to make the whole 100 g This composition was applied to dry, but not washed, hair.

After 2-3 minutes of contact, the hair was rinsed with water and then washed.

Soft, shiny and dull, well-dressed hair was obtained.

Example CC3 A hair cosmetic composition was prepared by blending the following components with the wax microdispersion.

 Prepared in Example C.

10% carnauba wax microdispersion 99.65 g methyl p-hydroxybenzoate 0.15 g imidazolidinyl urea derivative (manufactured by Sutton Labs, "GER
MALL 115 ") 0.20 g This composition was used in a manner similar to that described in Example CC1.

The hair after application of this composition had swelling, good hair styling and softness.

Example CC4 A pre-treatment composition for shampoo was prepared by blending the following components with the wax microdispersion.

97.5 g hydroxypropylcellulose (manufactured by Hercules, "KLUC
EL H ") 2.0 g methyl p-hydroxybenzoate 0.2 g imidazolidinyl urea derivative (manufactured by Sutton Labs," GER
MALL 115 ") 0.3 g This composition was applied to the hair under the conditions described in Example CC2. The treated hair was puffy, shiny and soft.

Example CC5 The following hair cosmetic composition was prepared by blending the following components with the wax microdispersion.

Wax microdispersion prepared in Example C 10 g "CARBOPOL 941" 1.5 g NaOH 0.6 g PEG-15 COCAMINE 3 g "GERMALL 115" 0.2 g Methyl p-hydroxybenzoate 0.2 g Potassium sorbate 0.3 g Flavor required Triethylamine Amount to make pH = 7 Water Amount to make the whole 100 g PEG-15 COCAMINE: CTFA (Cosmetic, Toiletry and Fra
ngrance Association) has defined it as a polyethylene glycol amine for copraic acid.
Product marketed under the product of OMEEN C25 ".

The composition was applied to dry and clean hair so that it spread well throughout the hair. The treated hair was puffy, shiny and well-dressed.

Claims (14)

(57) [Claims] (1) Formula (I): R-NHCOOCH (CH ₂ OCH ₂ CHOHCH ₂ OH) ₂ (I) wherein R is a saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms. A). 2. R is n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-decyl.
The compound according to claim 1, wherein the compound is selected from the group consisting of octadecenyl, 2-hexyldecyl, 2-octyldodecyl and 2-heptylundecyl groups. 3. The formula (IIA): R ₁ CH ₂ CH (R ₂ ) CH ₂ OCH ₂ CH (OR ₆ ) CH ₂ OCH ₂ CH (R ₂ ) CH ₂ R ₁
(II A) wherein R ₁ and R ₂ are taken together to form a group represented by the formula: —O—CR ₃ (R ₄ ) —O— (wherein R ₃ and R ₄ each represent a lower alkyl group; )), And R ₆ has the formula: And the amine RNH ₂ (R
Has the meaning as defined in claim 1) to obtain a compound of formula (III): R ₁ CH ₂ CH (R ₂ ) CH ₂ OCH ₂ CH (OR ₅ ) CH ₂ OCH ₂ CH (R ₂ ) CH ₂ R ₁
(III) (wherein, R ₁ and R ₂ have the above-mentioned meanings, and R ₅ is —CO—NHR
Wherein the corresponding compound of formula (I) is obtained by hydrolyzing the compound of formula (III) to obtain the corresponding compound of formula (I). 4. In the preparation of an aqueous wax microdispersion from a wax and the compound according to claim 1 as an emulsifier, the wax and the emulsifier are mixed with the wax, optionally in the presence of a part of water. Heating at a temperature above the melting point of but not exceeding 100 ° C. for a time until the wax is completely melted; at least while heating to the temperature at which the wax is molten, water or the balance of water Is continuously added and the resulting mixture is stirred until a wax microdispersion in the continuous aqueous phase is formed; and then the resulting wax microdispersion is cooled to ambient temperature, A method for producing an aqueous wax microdispersion. 5. The wax according to claim 4, wherein the wax is carnauba wax, candelilla wax, alpha wax or a mixture thereof.
The method described in. 6. The method according to claim 4, wherein the wax / emulsifier ratio is between 1 and 30. 7. Use for the preparation of a cosmetic composition comprising, in an aqueous vehicle, wax particles having a particle size of not more than 500 nm and at least one compound of the formula (I) as emulsifier. Stable wax microdispersion. 8. The dispersion according to claim 7, wherein the wax is selected from carnauba wax, candelilla wax, alpha wax or a mixture thereof. 9. A dispersion according to claim 7, wherein the emulsifier is present in an amount of from 0.01 to 25% by weight. 10. The dispersion according to claim 7, wherein the wax is present in an amount of 0.1 to 40% by weight. 11. The wax / emulsifier ratio is from 1 to 30,
A dispersion according to claim 7. 12. The method according to claim 1, wherein the surfactant or emulsifier is used.
A hair treatment cosmetic composition comprising at least one compound of the formula (I) according to the above. 13. The composition according to claim 12, wherein the compound of formula (I) is provided in the form of a wax microdispersion in an aqueous vehicle. 14. A surfactant or emulsifier comprising the compound of the formula (I) according to claim 1.